Recovery of hydrofluoric acid



March 13, 1 945. M. P. MATUszAK RECOVERY OF HYDROFLUORIC ACID I Filed Aug. e, 194s INVENToR MP. MATuszAK BYM i l A o Patented Mar. y13,1945

RECOVERY F mmRoFEUoRIc Acm Maryan P. Matuszak, Bartlesville, Okla.'l assignor to Phillips Petroleum Company, a corporation of f Delaware Application August c, 1943, `serial Nc. 497,637 12 claims. n (ci. 26o-683.4)

This invention relates to the recovery of hydrouoric acid. More particularly, it relates to the recovery of hydrouoric acid from homogeneous mixtures with low-boiling saturated aliphatic hydrocarbons by means of a heavy oleiinic oil readily separable from the low-boiling hydrocarbons.

Cormentrated or substantially anhydrous hydroiiuoric'acid is used in many modern processes. For exam'ple, it is used as a catalyst in the conversion of hydrocarbons by alkylation, isomerization, reconstruction, cracking, cyclization, and/or aromatization;- as a reactant vin the production of alkyl iiuorides; and as a scrubbing agent or selective solvent for the removal of certain impurities from saturated hydrocarbons. From such processes it is often necessary or convenient to Withdraw, for example, low-boiling or azeotropic mixtures of hydrouoric acid and saturated hydrocarbons. The corrosive nature oi hydrofluoric acid makes desirable its removal from such mixtures; in they past, removal has been commonly effected byneutralization of the acid with alkaline materials, -such as lime, but this procedure has the disadvantage that the acid becomes chemically bound and is lost to the process. Since in commercial processes the loss of hydrofluoric acid in such mixtures is economically signiiicant, recovery of the acid as such is desirable. l

Hydrofluoric acid used as a catalyst for alkylating purposes gradually becomes spent or deactivated, apparently'by dilution with acid-solubley by-products, to such a degree that it is no longer suited for continued use as an alkylation catalyst.

In consequence of this fact, a part of the acid isv i usually withdrawn continuously or intermittently from the alkylation step and ispurifled or recovered by fractional distillation and decomposition of organic fluorine compounds to liberate the fluorine as hydrouoric acid. The kettle product from such a recovery step is a heavy olenic oil of relatively high molecularweight.

An object of this invention is to recover hydrofluoric acid from homogeneous mixtures of hydroiluoric acid and low-boiling hydrocarbons.

Another object is to reduce the loss of hydrofluorlc acid in processes in which it is used as a catalyst. r

.Still another object is to utilize the heavy ole.- finic oil separated during regenerationof spent alkylation hydrouoric acid for the recovery of hydrofluoric acid froma mixture of hydrocarbons and hydroiluoric acid.

e Other objects and advantages of this invention will be apparent from the following description, i

the ,accompanyingdrawing and/or the appended claims. .l y

- According to one specific embodiment of this invention, hydrofluoric acid is recovered from a homogeneousy mixture with one or more saturated hydrocarbons bolingbelowabout F., such as parafiins having threertol i'lve carbon atoms per molecule,v by contacting the mixture, batchwlse orcontinuously, with a relatively heavy olefinic oil, preferably the heavy olenic oilrobtained as a kettle productfrom the distillationregeneration of used alkylation hydroiluoricacid, removing thelow-boiling hydrocarbons, and subjecting; the oil to a thermal decomposition-distillation whereby the hydrouoric acid is liberated and recovered assuch. Othersatisfactory olefinie oils are those containingoleflnic or unsaturated compounds that combine readily withv hydrogen fluoride at ordinary temperatures; among especially satisfactory oils are natural and synthetic terpenes, of which pinene and camphene are specific examples. Y Understanding of this invention may be facilitated lby reference to the accompanying drawing,

which isa schematic now diagram of one larrangement vof apparatus suitable for practicing the invention. For the sake of concreteness, this flow diagram illustrates the recovery of hydrofluoric acid invconnection with the' hydrofluoricl acid alkylation of an` alkylatable hydrocarbon with an alkylating agent.

yA hydrocarbon feed enters the system through I one or more inlets represented by inletw6 controlled byrvalve 'l and is passed to alkylator l0. This feed comprises an alkylatable hydrocarbon, which is usually an isoparaflin,` such as isobutane or isopentane, or an aromatic hydrocarbon, such as benzene, and an alkylatingvagent, which is usually one or more olens of three to five carbon atoms per molecule, such as the butylenes; itkalso generally comprises some relatively inert paraliins, suchas normal butane and propane. Concentrated or substantially anhydrous hydro'- uoric acid enters alkylator I0 through inlet 8 I controlled byvalve 9 and is intimately mixed with the hydrocarbon feed by any convenient means. The over-all mol ratio of alkylatable hydrocarbon lto olefin is usuallyfizl to 20:1- in the feed and much higher in thereaction zone. The

volume ratioof vhydrocarbons to acid in theA reaction zone is usually approximately 1:1, al-

though other ratios maybe maintained if desired.. Satisfactory operating conditions in alkylator. I0, for example, vfor the alkylation of yiso- .'butane'with olefins of three to four carbon atoms ture from alkylator l0 is passed through conduit ll controlled by valve I2 to settler or separator 20, in which it is separated into two liquid phases l by settling and/or centrifugation, aided, if desired, by cooling. acid phase is passed through Conduit 2|A controlled by valve 22 to hydroiluoricv acid-.regenerf ation means or still 30, wherein Yit is Yheated and/or fractionally distilled into the following fractions: a relatively large light fraction, comprising chiefly hydrouoric acid, dissolvedk iso.

butane and other low-boiling hydrocarbons, and A some low-boiling organic riluorine compounds, that is recycled through conduit 3| controlled by valveV 32 to alkylator t0; anda relatively small heavy or oit fraction boiling mostly above about 390F. and comprising chiefly acid-soluble olenic organic compounds of relatively high molecular weight, that is passed through conduit 33 to mixer B and/'or is withdrawn through outlet 3l in proportions controlled by valves 3-5 and 38, respectively.

.The lighter or hydrocarbon phase from separaterv 201s transferred through conduit 23 controlled by: valve 24 to `iractionating means M1 wherein itisl separted into various product, byproduct, and recycle fractions. A low-boiling orl azeotropic mixture of hydrofluoric acid and low-boiling parafns, such as propane and isobutane, is passed overhead through conduit M controlled byyalve 42 to mixer B0. A fraction consistingv predominantly of isobutane is recycled throug'lfil conduit 43 controlled by valve 44 to alkylator l0. A fraction comprising normal butane maybe withdrawn through outlet 45' controlled by valve 46;- if= desired, it may be passed to a dehydrogenation means, not sho-wn, in whichi-t is converted into olens that may be utilized as the alkyl-ating agent in alkylator t0. An alkylate fraction comprising highly branched normally liquid hydrocarbons suitable for use Yin aviation gasoline is passed' through conduit n controlled by valve 48 to defluorination means 50, in which it is substantially freed from organic fluorine v compounds by contact with a contact mass havingcataliytic hyd-rogenation and/ or dehydrogenation-properties, suc-h as'bauxite, alumina, chromi- 1 um oxide, or similar material,` at a temperature inthe range of `about 100 to 400@ F; and at a space velocity in the range ofabout l to 50 volurnes of liquid hydrocarbon material' per vol- `ume of contact mass per hour; the resulting uorine-free hydrocarbon material isthen passed through outlet 5l controlledV by valve 52i to storage or, if desired, to further processing means,

not; shown.

One aspect of the presen-t invention is concerned primarily: with the low-boiling or azeotropicv mixture of hydroluoric acid andlow-boiling parafns that isobtainedy as ani overhead fraction fromfractionating means 491. Ilhis fraction is thoroughly mixedinl mixer Bil with the heavy olenic oil` passed fromhydrofluoric acidregeneration means 30 through conduitI 33; Substantially .complete absorption. of' hydrouori'c acid;4 apparently by hydrofiuorination ot some The heavier or hydroiiuoric" vKil) of the; olenio compounds in the cil, takes place. t5

absorption or hydrouorination is substantially complete within 2 to 20 minutes; it appears to be catalytically initiated and/ or promoted by the presence of a trace of dissolved moisture, which accordingly may be advantageously added, as through inlet 3,' tcontro1led by valve 38. The optimum operating conditions for any particular case may be determined by trial by anyone skilled in the art. The resulting mixture of low-boiling parafns, absorbed hydroiluoric acid, and heavy oil is passed from mixer 61?, .to fractionator 1.0, in which it is separated intov two fractions: a sub,-` stantially acid-free light or overhead fraction consisting of the low-boiling paraiins, which is, removed through outlet 'Hi controlled by valve 12, and a heavy or kettle fraction consisting O f the acid-soluble oil and absorbed and/or chemically combined hydrofluoric acid. This kettle fraction may bel passed through conduit l' controlled by valve 'N to dehydroiiuorination means or still 8:0-, in which it is heated to about 30ill to. 35057 Fi., or more, as may be required to liberate substan= tifally all of the hydrofluoric acid; most of the hydrofluoric acid appears to be liberated below about 225 F. The liberated hydrofluoricacid may be withdrawn as an overhead traction through outlet 81 controlled by valve 82, or it may be recycled to alkylator IU by means not shown; Vthe resulting dehydrofluorinated oil may be recycled tol mixer 60, as through conduit. 83 controlled by val-ve 84, forre-use in recovering hydrofluori'c acid. Preferably, however, in the interest of reducing the over-all equipment by elimination of dehydrofluorination means 8U, the kettle fraction from ractionator T0 is passed through conduitfl controlled by valve 't6 toa suitable point in hydrouoric acid-regeneration means 3U, in which the hydroiluoric acid is liberated in similar fashion and from which it ifsy returned to alkylator I 0, as has been already described.

When', as sometimes may happen, the overhead fraction from fractionator- 'lill is' not substantially acid-free, it .may be subjected to one or more additional stages of mixing with heavy olenic oi=l andifractionation, in equip-ment similar tol or identical with mixer' 6o andv fractionator T0.'

When the mix-ture comprising hydrofluoric acid to be recovered contains anappreciable proportion of a di'icu-ltly condensable gas, such as methane or ethane, erw-hen it is under such con.- ditions that itis in the gaseous phase, mixer 6D may be conveniently a couhtercurrent extractor, wherein the heavy ole-nic oil absorbs the hyd-roiiuoricacid and wheref-rom the` acid-denudedgas is withdrawn; subsequent removar of dissolved low-boiling hydrocarbons andf/or ltberation of the hydrofluoric acid from the heavy.- oil extract'rnayA be practiced' as has been already described.

By: fractionating means, or similar terms, as usedf in this specification, isY meant a. system' of one or more fractional-distillation devices. that wiil' effect the results indicated; It will; be understbodf that numerous minor modications and variations of this invention will be obvious to those skilled in the art. The drawing is purely schematical; additional devices, such as pumps, valves, conduits, coolers, fractionators, etc., may be used in any particular case wherever they are deemed necessary or convenient for obtaining the results indicated, without passing beyond the scope of this invention or the spirit of this disclosure. l

Some aspects of the invention are further illustrated by the following example.

Example I A low-boiling mixture, comprising a major proportion by weight of low-boiling hydrocarbons, chiefly propane and isobutane, and a minor proportion of hydrofluoric acid, is obtained in 'a system for the hydroiiuoric acid alkylaticn of isobutane with oleiins of three to four carbon atoms per molecule. To this mixture is added a stoichiometrical excess 'of the heavy oleiinic oil obtained as a kettle product in the distillation-regeneration of spent hydroluoric acid (titratable acidity about 85 per cent by Weight) from the same alkylation system. The oil added is usually preferably 1.5 to 2 stoichiometric equivalents of the hydroiiuoric acid; but larger amounts may be used and have the advantage of making the absorption of hydrofluoric acid faster. `This oil appears to contain aliphatic and/or cyclic olens; one sample, which may be regarded as more or less typical, gave the following characterization data:

Gravity, A. P. I 16.2

Organic fluorine, wt. percent 0.1 A. S..T. M.type distillation, F.: l First drop 22 1 Cracking begins.

From the resulting mixture, 'the low-boiling hydrocarbons are removed by flashing and/or fractional distillation, and the residue is passed to the distillation-regeneration step, for liberation of the hydrofluoric acid, which is thereupon returned to the alkylaticn step for re-use as alkylaticn catalysts.

A similar procedure is useful for therecovery of hydrofluoric acid from other `homogeneous mixtures of low-boiling hydrocarbons and hydroiiuoric acid, such as those obtained in the various ing the hydrocarbons boiling below about 100 F., and heating the resulting residue to liberate and separate the hydrofluoric acid.

2. The process of claim 1, in which said homogeneous material is a low-boiling mixture of` paraiins of three to ve carbon atoms per mole,- cule and hydrolluoric acid.

3. The process of claim 1, in which said contacting is effected with said mixture in the liquid phase.

4. The process of claim l in which saidy olenic oil is the heavy olenic oil obtained ais a kettle product from the distillation-regeneration y of spent hydrofluoric acid used for the alkylaticn of an alkylatable hydrocarbon.

5. The process of claim 1 in which said olenic oil is the heavy oleiinic oil vobtained as a kettle product from the distillation-regeneration of spent hydroiiuoric acid used for the alkylaticn of isobutane.

6. The process of claim 1, in which the amount of olenic' compounds in said olefinic oil is 1.5 to

- 2 stoichiometric equivalents of said dissolved hyhydrofluoric acid-utilizing conversions and/or treatments hereinbefore mentioned. In particular, hydrofluoric acid-containing mixtures from pop-off valves or relief valves may be advantadrouoric acid. I

7. The process of claim 1, in'which said olenic oil comprises a terpene.

8. The process of claim 1, in which said contacting is effected in the presence of a trace of moisture.

f9. The process which comprises alkylating an f alkylatable hydrocarbon in the presence of liquid hydrouoric acid, separating the resulting alkylaticn mixture into a hydrocarbon liquid phase and a hydrouoric acid liquid phase, distilling from said hydrocarbon liquid phase a low-boiling fraction comprising a low-.boiling parafn and dissolved hydrofluoric acid, distilling said hydrouoric acid liquid phase to obtain therefrom a kettle product boiling above about 300 F., mixing saidlow-boiling fraction and said kettle product, distilling from the resulting mixture said f low-boiling parain, heating the resulting residue to liberate and distill therefrom hydroiluoric I, acid, and recycling the thus liberated hydrofluoric acid to the alkylaticn step.

10. The process of claim 1` in which said contacting is effected at a temperature of from 75 to 100 F.

11. The process whichcomprises alkylating an alkylatable hydrocarbon in the presenceof liquid hydrofluoric acid, separating the resulting alkylation mixture into a hydrocarbon liquid phase and a hydrofluoric acid liquid phase, distilling from said hydrocarbon liquid phase aglow-'boiling fraction comprising a low-boiling paraiin and dissolved hydrofluoric acid, distilling said hydrouoric acid liquid phase to obtain therefroma kettle product boiling above about 300 F., mixing said low-boiling fraction and said kettleproduct, distilling from the resulting mixture said low-boiling parain, passing the resulting residue to said step of distilling said hydrofluoric acid liquid phase and distilling said residue in admixture with said hydrouoric acid liquid phase to liberate and distill therefrom hydroiiuoric acid,

' and recycling the thus liberated hydrofluoric acid to the alkylaticn step.

12. The process of claim 1, in which said homogeneous mixture is in the gaseous phase and in .which said contacting is-eiected countercur- 1' rently.

\ MARYAN P. MATUSZAK. 

